Indoanilines in keratinic fiber dye cmpositions

ABSTRACT

Indoaniline of the formula ##SPC1##wherein R 1  represents hydrogen, halogen, alkyl or alkoxy; R 2  and R 3  represent alkyl; R 4 , R 5  and R 6  each independently represent hydrogen, halogen, alkyl, alkoxy, acylamino, ureido or carbalkoxyamino and R 5  can also represent amino, alkylamino, hydroxy alkylamino or carbamylalkylamino, the alkyl and alkoxy groups above being able to contain 1 to 6 carbon atoms and the acyl group from 2 to 7 carbon atoms with the condition that R 5  does not represent hydrogen, chlorine, methyl or methoxy and when R 5  represents acetylamino, R 6  does not represent hydrogen; it being understood that the above compounds can be present in the tautomeric form of that represented by formula (I). The indoaniline is usefully employed in dye compositions for keratinic fibers, especially living human hair.

The present invention relates to dialkylamine indoanilines of theformula ##SPC2##

Wherein R₁ represents hydrogen, halogen, alkyl or alkoxy; R₂ and R₃represent alkyl, R₄, R₅ and R₆ each independently represents hydrogen,halogen, alkyl, alkoxy, acylamino, ureido or carbalkoxy amino, R₅ analso represent amino, alkylamino, hydroxyalkylamino orcarbamylalkylamino, with the proviso the R₅ cannot represent hydrogen,chlorine, methyl or methoxy and when R₅ represents acetylamino, R₆ doesnot represent hydrogen (the above alkyl and alkoxy groups can containfrom 1 to 6 carbon atoms and the acyl group can obtain from 2 to 7carbon atoms). The present invention also relates to a process forpreparing these compounds and to the preparation of dye compositions forkeratinic fibers and in particular for living human hair containing saidcompounds. It will be appreciated that the above compounds can bepresent under tautomeric forms of that which is represented by formula(I).

Among the tautomer forms possible, one can cite the formula ##SPC3##

And when R₅ designates an amino, alkylamino, hydroxyalkylamino, orcarbamylalkylamino, the formula ##SPC4##

Wherein R₁ to R₆ have the meanings given above and R representshydrogen, alkyl, hydroxyalkyl, or carbamylalkyl.

The compounds of formula (I) can be prepared by condensing a compound ofthe formula ##SPC5##

Wherein Z represents NH₂, or NO when R₁ is in meta position relative tothe --NR₂ R₃ group, on a phenolic compound of the formula ##SPC6##

Wherein R₁, R₂, R₃, R₄, R₅ and R₆ have the meanings given above, or themeanings given below.

In a first method of preparation, when Z represents NH₂, one condensesthe phenolic compound of formula (III) on a paraphenylenediamine of theformula ##SPC7##

Wherein R₁ R₂ and R₃ have the meanings given above in an aqueousalkaline medium, in a hydroalcoholic medium, preferably hydroethanolicor hydroisopropanolic or in a hydroacetonic medium having a pH greaterthan 8 in the presence of an oxidizing agent and at a temperature ofabout 0°C.

The ratio of the phenolic compound to the paraphenylenediamine isbetween about 1:1 and 1:2, this ratio generally being about 1:1.

The oxidizing agent usefully employed in this condensation reaction canbe, for example, H₂ O₂, an alkaline persulfate, for example, thepersulfate of potassium or ammonium, an alkaline ferricyanide, forexample potassium ferricyanide. The quantity of the oxidizing agentemployed can vary from 1-5 times preferably 1-3 times the stoichiometricamount required for oxidizing the p-phenylenediamine to a quinonediimine.

As phenols, one can use 2-methyl-5-ureido phenol, 2-methyl-5-acetylaminophenol, 2-methyl-5-amino phenol, 2-methyl-5-methylamino phenol, 3-ureidophenol, 2,6-dimethyl-5-acetylamino phenol, 2,6-dimethyl-3-amino phenol,2,6-xylenol, 2-acetylamino phenol, meta-aminophenol,2,6-dimethyl-3-ureido phenol, 3-methoxy phenol, 3-acetylamino phenol,2-methyl-5-carbamylmethylaminophenol, 2,6-dimethyl phenol,2-methyl-5-carbethoxyamino phenol, 2,6-dimethyl-5-amino phenol,2-methyl-5-(N-β-hydroxyethylamino) phenol, 2,5-dimethyl phenol,2,3-xylenol, 2-ureido phenol, 2-chloro-5-amino phenol,2-chloro-5-acetylamino phenol and 3-chloro-6-acetylamino phenol.

As the paraphenylenediamines one can use, for instance, N,N-dimethylparaphenylenediamine, 2-methyl-4-N,N-diethylamino aniline,4-N,N-diethylamino-2-chloroaniline, 3-methoxy-4-amino-N,N-dimethylaniline, 3-chloro-4-amino-N,N-dimethyl aniline,3-methyl-4-amino-dimethyl aniline, N,N-diethyl-p-phenylenediamine,4-N,N-diethylamino-3-chloroaniline, 4-N,N-dimethylamino-3-chloroanilineand N,N-dibutyl-p-phenylenediamine.

The paraphenylenediamines can be replaced by one of their salts and inparticular by the hydrochloride, hydrobromide, sulfate or phosphatethereof.

In a second method of the present invention, when Z represents NO, onecondenses the phenolic compound of formula (III) on a nitroso derivativeof formula (V) ##SPC8## wherein R₁, R₂ and R₃ have the meanings givenabove. This condensation reaction is effected in an aqueous orhydroalcoholic medium preferably a hydroethanolic or ahydroisopropanolic medium at a temperature between about 30° and 60°C.,and preferably between 40° and 55°C.

Representative nitroso compounds that can usefully be employed include,4-nitroso-N,N-dibutylaniline, 3-chloro-4-nitroso diethylaniline and3-methoxy-4-nitroso-N,N-dimethylaniline.

The compounds wherein R₁ is in a position ortho relative to the --NR₂ R₃group and R₅ is amino can be obtained by hydrolysis using a base such asNaOH on the corresponding 3-acetylated derivative.

The indoanilines of formula (I), wherein R₁ represents hydrogen,halogen, alkyl or alkoxy; R₂ and R₃ represent alkyl; R₄, R₅ and R₆ eachindependently represents hydrogen, halogen, alkyl, alkoxy, acylamino,ureido, or carbalkoxyamino and R₅ can also designate amino, alkylamino,hydroxyalkylamino or carbamylalkylamino (the above alkyl groups beingable to contain 1 to 6 carbon atoms) with the proviso that R₅ does notrepresent hydrogen, chlorine, methoxy or methyl and when R₅ representsacetylamino, R₆ does not represent hydrogen, are new compounds.

Additionally, the following are new compounds:N-[(4'-diethylamino-2'-methyl)phenyl]-2,6-dimethyl benzoquinoneimine,

N-[(4'-diethylamino-2'-chloro)phenyl]-2-acetamino benzoquinoneimine,

N-[(4'-dimethylamino-2'-methyl)phenyl]-2,6-dimethyl benzoquinoneimine,

N-[(4'-dimethylamino-2'-chloro)phenyl]-2,6-dimethyl benzoquinoneimine,

N-[(4'-dimethylamino-2'-methoxy)phenyl]-2,6-dimethyl benzoquinoneimine,and

N-[(4'-dimethylamino-3'-chloro)phenyl]-2,6-dimethylbenzoquinoneimine.

The present invention also has for an object the dyes obtained by thecondensation of a compound of formula (II) on a compound of formula(III), as well as dyes obtained by the hydrolysis of a compoundacetylated in position 3 in the corresponding aminated dye.

The dyes find an interesting application in the dyeing of keratinicfibers and in particular of living human hair.

The present invention also has for an object a dye composition forkeratinic fibers, in particular for living human hair, characterized bythe fact that they include in an aqueous or hydroalcoholic solution, atleast one compound of formula (I) ##SPC9##

wherein R₁ represents hydrogen, halogen, alkyl or alkoxy; R₂ and R₃ eachindependently represents alkyl; R₄, R₅ and R₆ each independentlyrepresent hydrogen, halogen, alkyl, alkoxy, acylamino, ureido, orcarbalkoxyamino and R₅ can also represent amino, alkylamino,hydroxyalkylamino or carbamylalkylamino; it being understood that thealkyl groups can contain from 1 to 6 carbon atoms and the acyl groupscan contain from 2 to 7 carbon atoms.

These dye compositions include from 0.0075 to 2% and preferably from0.02 to 0.5% of the compound of formula (I) of the total weight of thecomposition.

The dye compositions according to the present invention can include onlythe indoanilines of formula (I).

It is, however, possible to mix the dyes according to the invention withother dyes conventionally utilized for the dyeing of hair, for examplenitro benzene dyes, azo dyes, anthraquinone dyes, indamines, indophenolsand/or other indoanilines.

The compositions according to the present invention are generallypresent in the form of an aqueous or hydroalcoholic solution containingone or more compounds of formula (I), in mixture or not with other dyes.They can, however, also include thickening agents and be present in theform of creams or gels.

To illustrate thickening agents that can be incorporated in the dyecompositions of the present invention, one can mention cellulosederivatives such as methylcellulose, hydroxyethylcellulose,carboxymethylcellulose or acrylic polymers such as the sodium salt ofpolyacrylic acid or carboxyvinyl polymers.

The dye compositions can include as solvents, water, lower alkanols,such as ethanol or isopropanol, polyalcohols such as glycols, forexample, ethyleneglycol, propyleneglycol, butylglycol, diethleneglycoland the monomethylether of diethyleneglycol.

The compositions according to the invention can also include variouscomponents conventionally utilized in cosmetic preparations, such aswetting agents, for example, oxyethylenated alkyl phenols,oxyethylenated fatty acids, oxyethylenated fatty alcohols, the sulfatesand sulfonates of fatty alcohols optionally oxyethylenated, dispersingagents, swelling agents, penetrating agents, emollients, polymers and/orperfumes. They can also be packaged in aerosol containers under pressurein the presence of a gaseous propellent,

One can use as the gaseous propellent, nitrogen, nitrous oxide, volatilehydrocarbons such as butane, isobutane, propane or preferably thefluoronated hydrocarbons sold under the name of FREON by Dupont, such adichlorodifluoromethane, 1,1-difluoromethane,1,2-dichloro-(1,1,2,2-tetrafluoromethane) or1-chloro-1,1-difluoromethane; a mixture of two or more hydrocarbons orfluoronated hydrocarbons can also be utilized.

The pH of the compositions can vary to a large extent. It is generallybetween about 4 to 11 and preferably between 6.5 and 10.5 andadvantageously between 7 and 9.

One can adjust the pH of the composition with an alkalizing agent forexample, ammonia, mono-, di- or triethanolamine, trisodium or disodiumphosphate, sodium or potassium carbonate or with an acidifying agent forexample, acetic acid, lactic acid, phosphoric acid, or citric acid.

The dyeing of keratinic fibers, in particular, living human hair, withthe dye compositions according to the present invention can be effectedin a conventional manner by applying the composition to the fibers to bedyed, permitting said composition to remain in contact therewith for aperiod varying from 5 to 30 minutes, followed by rinsing and eventuallywashing and drying the fibers.

The compositions according to the invention, when present in the form ofa hydroalcoholic solution, can also include a cosmetic film-formingresin and thus constitute a colored hair setting lotion which can beapplied to wet hair before the hair is set.

Representative cosmetic resins that can be employed in these hairsetting lotion compositions include polyvinyl pyrrolidone; copolymers ofvinylpyrrolidone and vinyl acetate; copolymers of vinyl acetate and anunsaturated carboxylic acid, such as crotonic acid; copolymers resultingfrom the copolymerization of vinyl acetate, crotonic acid and an acrylicor methacrylic ester; copolymers resulting from the copolymerization ofvinyl acetate and a vinyl alkyl ether; copolymers resulting from thecopolymerization of vinyl acetate, crotonic acid and a vinyl ester of along carbon chain acid or an acrylic or methacrylic ester of a longcarbon chain acid; copolymers resulting from the copolymerization of anester derived from an unsaturated alcohol and short carbon chain acid,from an unsaturated acid having a short carbon chain, and from at leastone ester derived from an unsaturated short chain alcohol and anunsaturated acid; and copolymers resulting from the copolymerization ofat least one unsaturated ester and at least one unsaturated acid.

Representative preferred resins include polyvinylpyrrolidone having amolecular weight from 10,000 to 160,000; copolymers of 10% crotonic acidand 90% vinyl acetate having a molecular weight from 10,000 to 70,000;copolymers of vinylpyrrolidone (VP) and vinyl acetate (VA) having amolecular weight of 30,000 to 200,000 the ratio of VP to VA beingbetween about 30:70 and 70:30, copolymers of maleic anhydride andmethylvinyl ether having a molar ratio of 1:1 and a specific viscosity,measured at 25°C. at a concentration of 1 gram in 100 cc of methylethylketone, between 0.1 and 3.5; the monoethyl ester, monoisopropyl esterand monobutyl ester of these copolymers of maleic anhydride andmethylvinyl ether; the copolymer of maleic anhydride and of butylvinylether having a mole ratio of 1:1; the terpolymers of methylmethacrylate(15 to 25%) -- stearylmethacrylate (18 to 28%) and dimethylmethacrylate(52 to 62%); and the terpolymers of vinyl acetate (75 to 85%) --allylstearate (10 to 20%) and allyloxyacetic acid (3 to 10%).

These resins are used generally in amounts between about 1 to 3% byweight of the total composition.

The alcohols employed to produce the hair setting lotions according tothe present invention are low molecular weight alcohols and preferablyare ethanol or isopropanol. These alcohols are generally used in amountsof about 20 to 70% by weight of the total composition.

The hair setting lotions according to the present invention can beemployed in a conventional manner by applying the same to living humanhair previously washed and rinsed, followed by rolling the same onrollers and then drying the hair.

The invention is illustrated by the following examples:

EXAMPLE I

Preparation of N-[(4'-dimethylamino)phenyl]-2-methyl-5-ureidobenzoquinoneimine. ##SPC10##

0.1 mole (16.6 grams) of 2-methyl-5-ureido phenol is dissolved in 400 ccof isopropyl alcohol to which have been added 400 cc of ammonia at 22°Be. To this solution, there is added 0.1 mole (20.9 grams) of thedihydrochloride of N,N-dimethyl paraphenylenediamine in 650 cc of water.After adding to this mixture 800 g of crushed ice, there is introduced,little by little, with good agitation and while maintaining thetemperature near 0°C., 0.2 mole (45.6 g) of ammonium persulfate in 150cc of water. At the end of this addition, the above indoaniline whichhas precipitated is filtered, washed with water, recrystallized in amixture of dimethylformamide and water and dried under a vacuum. Itexhibits a melting point of 275°C.

    ______________________________________                                                 Calculated For                                                       Analysis C.sub.16 H.sub.18 N.sub.4 O.sub.2                                                            Found                                                 ______________________________________                                        C%       64.41          64.29       64.44                                     H%        6.37           6.31        6.26                                     N%       18.78          19.01       18.93                                     ______________________________________                                    

EXAMPLE II

Preparation of N-λ(4'-dimethylamino)phenyl]-2-methyl-5-acetylaminobenzoquinoneimine. ##SPC11##

0.16 mole (26.4 g) of 2-methyl-5-acetylamino phenol is dissolved in 700cc of isopropanol to which have been added 800 cc of ammonia at 22° Be.To this solution, there is added 0.176 mole (36.8 g) of thedihydrochloride of N,N-dimethylparaphenylenediamine in 100 cc of waterand 1.3 kg of crushed ice. There is then added to the resulting mixture,whose temperature is maintained at about 0°C. little by little, and withagitation, 0.352 moles (80.25 g) of ammonium persulfate in 200 cc ofwater. At the end of this addition the above indoaniline which hasprecipitated is filtered, washed with water and recrystallized in amixture of dimethylformamide and water. The above product exhibits amelting point of 180°C.

    ______________________________________                                                     Calculated For                                                   Analysis     C.sub.17 H.sub.19 O.sub.2 N.sub.3                                                                Found                                         ______________________________________                                        C%           68.72              68.59                                         H%            6.39               6.59                                         N%           14.14              13.96                                         ______________________________________                                    

EXAMPLE III

Preparation of N-[(4'-dimethylamino)phenyl]-2-methyl-5-aminobenzoquinoneimine. ##SPC12##

0.2 mole (24.6 g) of 2-methyl-5-amino phenol is dissolved in 500 cc ofacetone to which have been added 200 cc of water and 500 cc of ammoniaat 22° Be. There are then added 500 g of crushed ice. Little by littleand with agitation, there are introduced into this reaction mixture,maintained at about 5°C. simultaneously with the aid of a double funnel,0.2 mole (41.8 g) of the dihydrochloride of N,N-dimethylparaphenylenediamine in 320 cc of water and 0.2 mole (45.8 g) ofammonium persulfate in 200 cc of water. At the end of this addition, theabove indoaniline, which has precipitated, is filtered, washed withwater, recrystallized in a mixture of dimethylformamide and water anddried under a vacuum. It exhibits a melting point of 255°C.

    ______________________________________                                                     Calculated For                                                   Analysis     C.sub.15 H.sub.17 ON.sub.3                                                                       Found                                         ______________________________________                                        C%           70.58              70.45                                         H%            6.66               6.82                                         N%           16.47              16.34                                         ______________________________________                                    

EXAMPLE IV

Preparation of N-[(4'-dimethylamino)phenyl] -2-methyl-5-methylaminobenzoquinoneimine. ##SPC13##

0.025 mole (3.42 g) of 2-methyl-5-methylamino phenol is dissolved in 100cc of water to which have been added 100 cc of ammonia at 22° Be. 150 gof crushed ice are then added to this solution. The resulting reactionmixture is maintained at a temperature of about 5°C. There are thenintroduced simultaneously, with good agitation and with the aid of adouble funnel, 0.025 mole (5.23 g) of the dihydrochloride ofN,N-dimethyl paraphenylenediamine in 50 cc of water and 0.025 mole (5.7g) of ammonium persulfate in 50 cc of water. The above indoaniline whichhas precipitated is then filtered, washed with water and recrystallizedin a mixture of dimethylformamide and water. After drying under avacuum, it exhibits a melting point of 202°C.

    ______________________________________                                                 Calculated For                                                       Analysis C.sub.16 H.sub.19 N.sub.3 O                                                                  Found                                                 ______________________________________                                        C%       71.34          71.23       71.19                                     H%        7.11           7.01        7.01                                     N%       15.60          15.61       15.73                                     ______________________________________                                    

EXAMPLE V

Preparation of N-[(4'-dimethylamino phenyl]-3-ureido benzoquinoneimine.##SPC14##

0.03 mole (4.56 g) of 3-ureido phenol is dissolved in 100 cc ofisopropyl alcohol to which have been added 100 cc of ammonia at 22° Be.350 g of crushed ice are then added to this solution. The resultingreaction mixture is maintained at about 0° C., and there are introducedsimultaneously, with good agitation and with the aid of a double funnel0.03 mole (6.27 g) of the dihydrochloride of N,N-dimethylparaphenylenediamine in 50 cc of water and 0.060 mole (13.7 g) ofammonium persulfate in 50 cc of water. At the end of this addition, theagitation is continued for 15 minutes and the above indoaniline which asprecipitated is then filtered, washed with water, recrystallized in amixture of dimethylformamide in water and dried under a vacuum. Itexhibits a melting point of 226° C.

    ______________________________________                                                 Calculated For                                                       Analysis C.sub.15 H.sub.16 N.sub.4 O.sub.2                                                            Found                                                 ______________________________________                                        C%       63.36          63.45       63.52                                     H%        5.67           5.77        5.83                                     N%       19.71          19.88       19.72                                     ______________________________________                                    

EXAMPLE VI

Preparation of N-[(4'-dimethylamino) phenyl]-2,6-dimethyl-3-acetylaminobenzoquinoneimine. ##SPC15##

0.3 mole (53.7 g) of 2,6-dimethyl-3-acetylamino phenol is dissolved in400 cc of acetone to which have been added 400 cc of ammonia at 22° Be.The resulting mixture is maintained at a temperature of about 10°C., andthere are introduced therein simultaneously, with the aid of a doublefunnel, 0.3 mole (62.7 g) of the dihydrochloride of N,N-dimethylparaphenylenediamine in 500 cc of water and 0.6 mole (137 g) of ammoniumpersulfate in 500 cc of water. The above indoaniline which precipitatesis then filtered, washed with water, recrystallized in a mixture ofdimethylformamide and water and dried under a vacuum. It exhibits amelting point of 111°C.

    ______________________________________                                                 Calculated For                                                       Analysis C.sub.18 H.sub.21 O.sub.2 N.sub.3                                                            Found                                                 ______________________________________                                        C%       69.43          69.13       69.25                                     H%        6.80           6.64        6.74                                     N%       13.50          13.72       13.60                                     ______________________________________                                    

EXAMPLE VII

Preparation of N-[(4'-dimethylamino) phenyl]-2,6-dimethyl-3-aminobenzoquinoneimine. ##SPC16##

0.4 mole (69.4 g) of 2,6-dimethyl-3-amino phenol is dissolved in 1 literof acetone to which has been added 1 liter of ammonia at 22°Be. 1 kg ofcrushed ice is then added to this solution and then with the aid of adouble funnel, there are introduced simultaneously, with good agitation,0.4 mole (83.6 g) of the dihydrochloride ofN,N-dimethylparaphenylenediamine in 1 liter of water and 0.44 mole (100g) of ammonium persulfate in 800 cc of water. The temperature of thereaction mixture is maintained at about 0°C. At the end of the addition,the raw product is filtered, washed with water and recrystallized in amixture of dimethylformamide and water. After drying under a vacuum, theabove indoaniline exhibits a melting point of 178°C.

    ______________________________________                                                 Calculated For                                                       Analysis C.sub.16 H.sub.19 ON.sub.3                                                                   Found                                                 ______________________________________                                        C%       71.34          71.41       71.57                                     H%        7.11           7.19        7.26                                     N%       15.60          15.45       15.57                                     ______________________________________                                    

EXAMPLE VIII

Preparation of N-[(4'-diethylamino-2'-methyl) phenyl]-2,6-dimethylbenzoquinoneimine. ##SPC17##

0.01 mole (2.51 g) of the dihydrochloride of 2-methyl-4-N,N-diethylaminoaniline and 0.01 mole (1.22 g) of 2,6-xylenol are dissolved in 85 cc ofnormal sodium hydroxide solution to which have been added 20 cc ofethanol. Little by little, to this solution, with agitation and whilemaintaining the temperature near about 0°C., there is added 0.02 mole(4.56 g) of ammonium persulfate in 46 cc of water. The raw indoanilineabove is filtered, washed with water and recrystallized in a mixture ofwater and acetone. After drying under a vacuum, the product exhibits amelting point of 128°C.

    ______________________________________                                                 Calculated For                                                       Analysis C.sub.19 H.sub.24 N.sub.2 O                                                                  Found                                                 ______________________________________                                        C%       76.99          76.83       76.76                                     H%       8.16           8.05        8.19                                      N%       9.45           9.32        9.54                                      ______________________________________                                    

EXAMPLE IX

Preparation of N-[(4'-diethylamino-2'-chloro) phenyl]-2-acetaminobenzoquinoneimine. ##SPC18##

0.01 mole (1.51 g) of 2-acetylamino phenol is dissolved in 25 cc ofisopropyl alcohol to which have been added 25 cc of ammonia at 22° Be.There are then added 50 g of crushed ice. The resulting mixture ismaintained at a temperature of about 0°C., and there are then introducedsimultaneously with agitation, 0.01, mole (2.71 g) of thedihydrochloride of 2-chloro-4-N,N-diethylamino aniline in 20 cc of waterand 0.02 mole (4.46 g) of ammonium persulfate in 25 cc of water. At theend of this addition, the above indoaniline which precipitates isfiltered, washed with water, recrystallized in dimethylformamide, anddried under a vacuum. The product exhibits a melting point of 155°C.

    ______________________________________                                                 Calculated For                                                       Analysis C.sub.18 H.sub.20 N.sub.3 ClO.sub.2                                                          Found                                                 ______________________________________                                        C%       62.51          62.76       62.75                                     H%        5.80           5.95        5.95                                     N%       12.18          12.16       12.32                                     ______________________________________                                    

EXAMPLE X

Preparation of N-[(4'-dimethylamino) phenyl]-3-amino benzoquinoneimine.##SPC19##

0.01 mole (2.09 g) of the dihydrochloride ofN,N-dimethylparaphenylenediamine and, 0.01 mole (1.09 g) ofmethaaminophenol are dissolved in 40 cc of water to which have beenadded 7 cc of ammonia at 22° Be. To this solution, cooled to 0°C., thereare added 20 cc of H₂ O₂ (20 volumes). The resulting reaction mixture isleft to stand for 24 hours at ambient temperature. The raw product whichhas precipitated is then filtered, washed with water and dried under avacuum. This raw product is then extracted 4 times with 100 cc of ether,at 20°C. The etherified extracts are then combined and concentratedunder a vacuum to a volume of about 10 cc. After cooling, the aboveindoaniline which has crystallized is filtered, recrystallized indimethylformamide and dried under a vacuum. The product exhibits amelting point of 171°C., and is chromatographically pure. Molecular masscalculated for C₁₄ H₁₅ N₃ O : 241. molecular mass found bypotentiometric dosage effected in methylisobutylketone with perchloricacid : 240.

    ______________________________________                                                 Calculated For                                                       Analysis C.sub.14 H.sub.15 N.sub.3 O                                                                  Found                                                 ______________________________________                                        C%       69.69          69.58       69.46                                     H%        6.27           6.26        6.27                                     N%       17.42          17.70       17.64                                     ______________________________________                                    

EXAMPLE XI

Preparation of N-[(4'-dimethylamino) phenyl]-2,6-dimethyl-5-ureidobenzoquinoneimine. ##SPC20##

0.2 mole (36 g) of 2,6-dimethyl-3-ureido phenol is dissolved in 1 literof isopropyl alcohol to which have been added 800 cc of ammonia at 22°Be. There are then added 800 g of crushed ice to this reaction mixture.Then, little by little and with good agitation, there are introducedsimultaneously, 0.2 mole (41 g) of the dihydrochloride ofN,N-dimethylparaphenylenediamine in 500 cc of water and 0.4 mole (92 g)of ammonium persulfate in 500 cc of water. During the time of theseadditions, the temperature of the reaction mixture is maintained atabout 0°C. At the end of these additions, the above indoaniline isfiltered, washed with water and dried under a vacuum. The product ischromatographically pure and melts at a temperature of 245°C.

    ______________________________________                                                 Calculated For                                                       Analysis C.sub.17 H.sub.20 N.sub.4 O.sub.2                                                            Found                                                 ______________________________________                                        C%       65.36          65.60       65.61                                     H%        6.45           6.55        6.57                                     N%       17.94          18.08       17.97                                     ______________________________________                                    

EXAMPLE XII

Preparation of N-[(4'-dibutylamino)phenyl]-2-methyl-5-carbamylmethylamino benzoquinoneimine. ##SPC21##

0.01 mole (2.7 g) of the hydrochloride of 4-nitroso-N,N-dibutylanilineand 0.01 (1.80 g) of 2-methyl-5-carbamylmethylamino phenol are dissolvedin 30 cc of a 50% hydroethanolic solution. The resulting reactionmixture is stirred for a period of 1 hour at 40°C. The above rawindoaniline which has precipitated is then filtered and dissolved in 10cc of dimethylformamide at ambient temperature. After filtration, inorder to eliminate secondary insoluble products formed in a minorquantity, there are added 10 ml of water to reprecipitate theindoaniline which is then filtered, washed with water and dried under avacuum. The product is chromatographically pure and melts at 169°C.

    ______________________________________                                                 Calculated For                                                       Analysis C.sub.23 H.sub.32 N.sub.4 O.sub.2                                                            Found                                                 ______________________________________                                        C%       69.66          69.80       69.68                                     H%        8.13           8.23        8.26                                     N%       14.13          14.04       13.98                                     ______________________________________                                    

EXAMPLE XIII

Preparation ofN-[(4'-diethylamino-2'-chloro)phenyl]-2,6-dimethyl-3-aminobenzoquinoneimine. ##SPC22##

Into 30 cc of ethanol to which have been added 20 cc of a normal sodiumhydroxide solution, there are introduced 0.01 mole (2.12 g) of3-chloro-4-nitroso diethylaniline and 0.011 mole (1.91 g) of thehydrochloride of 2,6-dimethyl-3-amino phenol. The mixture is maintainedwith agitation for 4 hours at 35°C. The above indoaniline is thenfiltered, washed several times with water at 50°C., and recrystallizedin a mixture of dimethylformamide in water. The product exhibits amelting point of 160°C.

    ______________________________________                                                 Calculated For                                                       Analysis C.sub.18 H.sub.22 N.sub.3 ClO                                                                Found                                                 ______________________________________                                        C%       65.15          65.04       65.14                                     H%        6.65           6.72        6.74                                     N%       12.67          12.73       12.69                                     Cl%      10.70          10.84       10.92                                     ______________________________________                                    

EXAMPLE XIV

Preparation of N-[(4'-dimethylamino) phenyl]-2-chloro-5-aminobenzoquinoneimine. ##SPC23##

0.01 mole (2.09 g) of the dihydrochloride ofN,N-dimethylparaphenylenediamine and 0.01 mole (1.43 g) of2-chloro-5-amino phenol are dissolved in 150 cc of a 0.7 N sodiumhydroxide solution. To this solution, cooled to 0°C., there is added,little by little, with agitation, 0.02 mole (4.60 g) of ammoniumpersulfate in solution in 20 cc of water. At the end of this addition,the agitation of the mixture is continued for additional 15 minutes. Theabove indoaniline which precipitates is filtered, washed with water andthen with acetone. The raw product is dissolved in dimethylformamide at0°C., (10 cc of dimethylformamide per gram of raw product). Theresulting solution is then filtered to eliminate a slightly insolublewhite product. After cooling the filtrate to 0°C., the above indoanilinecrystallizes in the form of reddish-brown flakes having golden glints.These flakes are filtered and dried under a vacuum. After drying, theproduct exhibits a melting point of 242°C.

    ______________________________________                                                 Calculated For                                                       Analysis C.sub.14 H.sub.14 N.sub.3 ClO                                                                Found                                                 ______________________________________                                        C%       60.98          61.09       60.92                                     H%        5.09           5.00        4.96                                     N%       15.24          15.40       15.21                                     Cl%      12.87          12.93       13.02                                     ______________________________________                                    

EXAMPLE XV

Preparation of N-[(4'-dimethylamino-2'-methyl) phenyl]-2,6-dimethylbenzoquinoneimine. ##SPC24##

0.01 mole (1.22 g) of 2,6-dimethyl phenol is dissolved in 20 cc ofacetone, 5 cc of water and 15 cc of ammonia (22° Be). To this solution,maintained at a temperature of about +5°C, there are added, little bylittle, with agitation, and simultaneously with the aid of a doublefunnel, 0.01 mole (2.23 g) of the dihydrochloride of3-methyl-4-amino-N,N-dimethylaniline dissolved in 15 cc of water and0.02 mole (4.6 g) of ammonium persulfate dissolved in 20 cc of water. Atthe end of these additions, the stirring of the reaction mixture iscontinued for one hour at ambient temperature. The above indoanilinewhich has precipitated is then filtered, washed with water,recrystallized in a mixture of dimethylformamide and water and driedunder a vacuum. It exhibits a melting point of 157°C.

    ______________________________________                                                     Calculated For                                                   Analysis     C.sub.17 H.sub.20 N.sub.2 O                                                                      Found                                         ______________________________________                                        C%           76.08              75.95                                         H%            7.51               7.51                                         N%           10.44              10.46                                         ______________________________________                                    

EXAMPLE XVI

Preparation of N-[(4'-dimethylamino-2'-chloro) phenyl]-2,6-dimethylbenzoquinoneimine. ##SPC25##

0.01 mole (1.22 g) of 2,6-dimethyl phenol and 0.01 mole (2.44 g) of thedihydrochloride of 3-chloro-4-amino-N,N-dimethylaniline are dissolved in20 cc of acetone, 15 cc of water and 15 cc of amonia (22° Be). To thisresulting solution, cooled to about +5°C, there is added, little bylittle, with agitation, 0.02 mole of ammonium persulfate dissolved in 20cc of water. At the end of this addition, the stirring is continued for30 minutes. The above indoaniline which has precipitated is filtered,washed with water and dried under a vacuum. It exhibits a melting pointof 154°C.

    ______________________________________                                                     Calculated For                                                   Analysis     C.sub.16 H.sub.17 ClN.sub.2 O                                                                    Found                                         ______________________________________                                        C%           66.19              66.04                                         H%            5.58               5.80                                         N%            9.70               9.74                                         Cl%          12.27              12.14                                         ______________________________________                                    

EXAMPLE XVII

Preparation of N-[(4'-dimethylamino-2'-methoxy) phenyl]-2,6-dimethylbenzoquinoneimine. ##SPC26##

0.01 mole (2.64 g) of 3-methoxy-4-amino-N,N-dimethylaniline sulfate and0.01 mole (1.22 g) of 2,6-dimethyl phenol are dissolved in 20 cc ofwater, 35 cc of acetone and 10 cc of ammonia; (22° Be). To the resultingsolution, cooled in ice, there is added, little by little, withagitation, 0.02 mole (4.6 g) of ammonium persulfate in 20 cc of water.At the end of this addition the stirring of the reaction mixture iscontinued for one hour. The above indoaniline which has precipitated isthen filtered, washed first with water and then with acetone and driedunder a vacuum. It exhibits a melting point of 140°C.

    ______________________________________                                                     Calculated For                                                   Analysis     C.sub.17 H.sub.20 N.sub.2 O.sub.2                                                                Found                                         ______________________________________                                        C%           71.80              71.60                                         H%           7.09               7.06                                          N%           9.85               9.99                                          ______________________________________                                    

EXAMPLE XVIII

Preparation of N-[(4'-dimethylamino-2'-methyl) phenyl]-6-methyl-3-aminobenzoquinoneimine. ##SPC27##

0.02 mole (2.46 g) of 2-methyl-5-amino phenol is dissolved in 40 cc ofacetone, 10 cc of ice and 30 cc of ammonia (22° Be). To the resultingsolution, maintained at a temperature of about +5°C., there are added,little by little, with agitation and simultaneously with the aid of adouble funnel, 0.02 mole (4.46 g) of the dihydrochloride of3-methyl-4-amino-N,N-dimethylaniline dissolved in 25 cc of water and0.02 mole (4.6 g) of ammonium persulfate dissolved in 10 cc of water. Atthe end of this addition, the stirring of the reaction mixture iscontinued for one hour at ambient temperature. The above indoanilinewhich has precipitated is then filtered, washed with water,recrystallized in a mixture of dimethylformamide and water under avacuum. It exhibits a melting point of 200°C.

    ______________________________________                                                     Calculated For                                                   Analysis     C.sub.16 H.sub.19 N.sub.3 O                                                                      Found                                         ______________________________________                                        C%           71.34              71.41                                         H%            7.11               7.37                                         N%           15.60              15.79                                         ______________________________________                                    

EXAMPLE XIX

Preparation of N-[(4'-dimethylamino-2'-methoxy-)phenyl]-6-methyl-3-amino benzoquinoneimine. ##SPC28##

0.012 mole (3.2 g) of 3-methoxy-4-amino-N,N-dimethylaniline sulfate and0.02 mole (2.46 g) of 2-methyl-5-amino phenol are dissolved in 60 cc ofa 50% hydroacetonic solution to which have been added 20 cc of ammonia(22° Be). To the resulting solution, maintained at a temperature ofabout 0°C., there is added, little by little, with agitation, 0.02 mole(4.6 g) of ammonium persulfate dissolved in 20 cc of water. At the endof this addition, stirring of the reaction mixture is continued for onehour at 0°C. The above indoaniline which has precipitated is thenfiltered, washed first with water and then with a normal NaOH solutionto eliminate the 2-methyl-5-amino phenol that it contains, and finallywith water. After recrystallization in a mixture of dimethylformamideand water and drying under a vacuum, the product exhibits a meltingpoint of 168°C.

    ______________________________________                                                     Calculated For                                                   Analysis     C.sub.16 H.sub.19 N.sub.3 O.sub.2                                                                Found                                         ______________________________________                                        C%           67.34              67.32                                         H%            6.71               6.77                                         N%           14.73              14.58                                         ______________________________________                                    

EXAMPLE XX

Preparation of N-[(4'-dimethylamino-2'-chloro)phenyl]-6-methyl-3-acetylamino benzoquinoneimine. ##SPC29##

0.01 mole (1.65 g) of 2-methyl-5-acetylamino phenol and 0.01 mole (2.44g) of the dihydrochloride of 3-chloro-4-amino-N,N-dimethylaniline aredissolved in 20 cc of acetone to which have been added 15 cc of waterand 15 cc of ammonia (22°Be). To the resulting solution, maintained at atemperature of about +5°C., there is added, little by little, withagitation, 0.02 mole (4.6 g) of ammonium persulfate in 20 cc of water.At the end of this addition, the stirring of the reaction mixture iscontinued for 30 minutes. The above indoaniline which precipitates isthen filtered, washed with water, recrystallized in a mixture ofdimethylformamide and water and dried under a vacuum. It exhibits amelting point of 178°C.

    ______________________________________                                                     Calculated For                                                   Analysis     C.sub.17 H.sub.18 ClN.sub.3 O.sub.2                                                              Found                                         ______________________________________                                        C%           61.53              61.30                                         H%            5.46               5.15                                         N%           12.66              12.38                                         Cl%          10.68              10.43                                         ______________________________________                                    

EXAMPLE XXI

Preparation of N-[(4'-dimethylamino-2'-chloro) phenyl]-6-methyl-3-aminobenzoquinoneimine. ##SPC30##

0.01 mole (1.23 g) of 2-methyl-5-amino phenol is dissolved in 10 cc ofacetone to which have been added 5 cc of water and 15 cc of ammonia(22°Be). To the resulting solution, cooled to about +5°C., there areadded, little by little, with agitation and simultaneously with the useof a double funnel, 0.01 mole (2.44 g) of the dihydrochloride of3-chloro-4-amino-N,N-dimethylaniline dissolved in 15 cc of water, and0.01 mole (2.3 g) of ammonium persulfate dissolved in 10 cc of water. Atthe end of this addition, the stirring of the reaction mixture iscontinued for 30 minutes. The above indoaniline which has precipitatedin the form of crystals is then filtered, washed with water,recrystallized in a mixture of dimethylformamide and water and driedunder a vacuum. It exhibits a melting point of 203°C.

    ______________________________________                                                     Calculated For                                                   Analysis     C.sub.15 H.sub.16 ClN.sub.3 O                                                                    Found                                         ______________________________________                                        C%           62.16              62.33                                         H%            5.56               5.42                                         N%           14.50              14.40                                         Cl%          12.23              12.32                                         ______________________________________                                    

EXAMPLE XXII

Preparation of N-[(4°-dimethylamino-2'-methyl)phenyl]-6-methyl-3-acetylamino benzoquinoneimine. ##SPC31##

0.01 mole (1.65 g) of 2-methyl-5-acetylamino phenol is dissolved in 20cc of acetone, 5 cc of water and 15 cc of ammonia (22°Be). To theresulting solution, maintained at a temperature of about +5°C., thereare added, little by little, with agitation and simultaneously with theaid of a double funnel, 0.01 mole (2.23 g) of the dihydrochloride of3-methyl-4-amino-N,N-dimethyl aniline dissolved in 15 cc of water, and0.02 mole (4.6 g) of ammonium persulfate dissolved in 20 cc of water. Atthe end of this addition, the stirring of the reaction mixture iscontinued for one hour. The above indoaniline which has precipitated inthe form of crystals, is filtered, washed with water, recrystallized ina mixture of dimethylformamide and water and dried under a vacuum. Itexhibits a melting point of 182°C.

    ______________________________________                                                     Calculated For                                                   Analysis     C.sub.18 H.sub.21 N.sub.3 O.sub.2                                                                Found                                         ______________________________________                                        C%           69.43              69.13                                         H%            6.80               6.88                                         N%           13.50              13.69                                         ______________________________________                                    

EXAMPLE XXIII

Preparation of N-[(4'-dimethylamino-2'-methoxy)phenyl]-6-methyl-3-acetylamino benzoquinoneimine. ##SPC32##

0.01 mole (1.65 g) of 2-methyl-5-acetylamino phenol is dissolved in 50cc of a 0.6 N NaOH solution. To the resulting solution, cooled to 0°C.,there are added, little by little, with agitation and simultaneouslywith the aid of a double funnel, 0.01 mole (2.64 g) of3-methoxy-4-amino-N,N-dimethylaniline sulfate dissolved in 20 cc ofwater, and 0.02 mole (4.6 g) of ammonium persulfate dissolved in 20 ccof water to which have been added 5 cc of ammonia (22°Be). At the end ofthis addition, the stirring of the reaction mixture is continued for 15minutes. The above indoaniline which has precipitated is then filtered,washed with water, recrystallized in a mixture of dimethylformamide andwater and dried under a vacuum at 80°C. It exhibits a melting point of184°C.

    ______________________________________                                                     Calculated For                                                   Analysis     C.sub.18 H.sub.21 N.sub.3 O.sub.3                                                                Found                                         ______________________________________                                        C%           66.03              65.82                                         H%            6.47               6.60                                         N%           12.84              13.02                                         ______________________________________                                    

EXAMPLE XXIV

Preparation of N-[(4'-dimethylamino-2'-methoxy)phenyl]-6-methyl-3-carbethoxyamino benzoquinoneimine. ##SPC33##

0.02 mole (5.28 g) of 3-methoxy-4-amino-N,N-dimethylaniline sulfate and0.02 mole (3.9 g) of 2-methyl-5-carbethoxyamino phenol are dissolved in25 cc of acetone, 50 cc of water and 15 cc of ammonia (22°Be). To theresulting solution, cooled to about 0°C., there is added, little bylittle, with agitation, 0.04 mole (9.2 g) of ammonium persulfatedissolved in 40 cc of water. At the end of this addition, stirring ofthe reaction mixture is continued for 30 minutes. The above indoanilinewhich has precipitated in the form of crystals is filtered, washed withwater, recrystallized in a mixture of dimethylformamide and water anddried under a vacuum at 100°C. It exhibits a melting point of 182°C.

    ______________________________________                                                     Calculated For                                                   Analysis     C.sub.19 H.sub.23 N.sub.3 O.sub.4                                                                Found                                         ______________________________________                                        C%           63.85              63.88                                         H%            6.48               6.39                                         N%           11.76              11.80                                         ______________________________________                                    

EXAMPLE XXV

Preparation of N-[(4'-dimethylamino-2'-methyl)phenyl]-2,6-dimethyl-3-amino benzoquinoneimine. ##SPC34##

0.02 mole (3.47 g) of the hydrochloride of 2,6-dimethyl-5-amino phenolis dissolved in 40 cc of acetone, 10 cc of water and 30 cc of ammonia(22° Be). To the resulting solution, maintained at a temperature ofabout +5°C., there are added, little by little, with agitation andsimultaneously with the aid of a double funnel, 0.02 mole (4.46 g) ofthe dihydrochloride of 3-methyl-4-amino-N,N-dimethylaniline dissolved in25 cc of water, and 0.02 mole (4.60 g) of ammonium persulfate dissolvedin 20 cc of water. At the end of these additions, stirring of thereaction mixture is continued for one hour at ambient temperature. Theabove indoaniline which has precipitated in the form of crystals isfiltered, washed with water, recrystallized in a mixture ofdimethylformamide and water and dried under a vacuum. It exhibits amelting point of 170°C.

    ______________________________________                                                     Calculated For                                                   Analysis     C.sub.17 H.sub.21 N.sub.3 O                                                                      Found                                         ______________________________________                                        C%           72.05              71.85                                         H%            7.47               7.22                                         N%           14.83              14.90                                         ______________________________________                                    

EXAMPLE XXVI

Preparation of N-[(4'-dimethylamino-2'-chloro)phenyl]-2,6-dimethyl-3-amino benzoquinoneimine. ##SPC35##

0.02 mole (3.5 g) of the hydrochloride of 2,6-dimethyl-5-amino phenoland 0.022 mole (5.36 g) of the dihydrochloride of3-chloro-4-amino-N,N-dimethylaniline are dissolved in 50 cc of acetone,40 cc of water and 40 cc of ammonia (22°Be). To the resulting solutionthere are added 100 cc of H₂ O₂ (20 volumes) and the resulting mixtureis left to stand for 6 hours at ambient temperature. The aboveindoaniline which has precipitated in the form of crystals is thenfiltered, washed with water and dried under a vacuum. It exhibits amelting point of 183°C.

    ______________________________________                                                     Calculated For                                                   Analysis     C.sub.16 H.sub.18 ClN.sub.3 O                                                                    Found                                         ______________________________________                                        C%           63.25              63.16                                         H%            5.97               6.00                                         N%           13.83              13.98                                         Cl%          11.67              11.79                                         ______________________________________                                    

EXAMPLE XXVII

Preparation of N-[(4'-dimethylamino-2'-methoxy)phenyl]-2,6-dimethyl-3-amino benzoquinoneimine. ##SPC36##

Into 50 cc of a 0.6 N NaOH solution to which have been added 20 cc ofethanol, there are introduced 0.02 mole (3.6 g) of3-methoxy-4-nitroso-N,N-dimethylaniline and 0.022 mole (3.9 g) of thehydrochloride of 2,6-dimethyl-5-amino phenol. The resulting reactionmixture is stirred for one hour at 50°C. The above indoaniline whichprecipitates is then filtered and washed several times with water at50°C., and then with acetone. After recrystallization in ethylacetateand drying under a vacuum, it exhibits a melting point of 152°C.

    ______________________________________                                                     Calculated For                                                   Analysis     C.sub.17 H.sub.21 N.sub.3 O.sub.2                                                                Found                                         ______________________________________                                        C%           68.20              68.09                                         H%            7.07               7.21                                         N%           14.04              14.23                                         ______________________________________                                    

EXAMPLE XXVIII

Preparation of N-[(4'-dimethylamino-2'-methyl)phenyl]-2,6-dimethyl-3-acetylamino benzoquinoneimine. ##SPC37##

0.01 mole (1.79 g) of 2,6-dimethyl-5-acetylamino phenol is dissolved in20 cc of acetone, 5 cc of water and 15 cc of ammonia (22°Be). To theresulting solution, maintained at a temperature of about +5°C., thereare added, little by little, with agitation and simultaneously with theaid of a double funnel, 0.01 mole (2.23 g) of the dihydrochloride of3-methyl-4-amino-N,N-dimethylaniline dissolved in 15 cc of water, and0.02 mole (4.6 g) of ammonium persulfate dissolved in 20 cc of water. Atthe end of these additions, the stirring of the reaction mixture iscontinued for one hour at ambient temperature. The above indoanilinewhich has precipitated is then filtered, washed with water,recrystallized in a mixture of dimethylformamide and water and driedunder a vacuum. It exhibits a melting point of 184°C.

    ______________________________________                                                     Calculated For                                                   Analysis     C.sub.19 H.sub.23 N.sub.3 O.sub.2                                                                Found                                         ______________________________________                                        C%           70.13              70.00                                         H%            7.12               7.42                                         N%           12.91              13.01                                         ______________________________________                                    

EXAMPLE XXIX

Preparation of N-[(4'-dimethylamino-2'-chloro)phenyl]-2,6-dimethyl-3-acetylamino benzoquinoneimine. ##SPC38##

0.01 mole (1.79 g) of 2,6-dimethyl-5-acetylamino phenol and 0.01 mole(2.44 g) of the dihydrochloride of 3-chloro-4-amino-N,N-dimethylanilineare dissolved in 20 cc of acetone, 15 cc of water and 15 cc of ammonia(22°Be). To the resulting solution, cooled to about +5°C., there isadded, little by little, with agitation, 0.02 mole (4.6 g) of ammoniumpersulfate dissolved in 20 cc of water. At the end of this addition, thestirring of the reaction mixture is continued for 30 minutes. The aboveindoaniline which has precipitated is then filtered, washed with water,recrystallized in a mixture of dimethylformamide and water and diredunder a vacuum at 100°C. It exhibits a melting point of 182°C.

    ______________________________________                                                     Calculated For                                                   Analysis     C.sub.18 H.sub.20 ClN.sub.3 O.sub.2                                                              Found                                         ______________________________________                                        C%           62.52              62.58                                         H%            5.83               6.00                                         N%           12.15              12.33                                         Cl%          10.25              10.00                                         ______________________________________                                    

EXAMPLE XXX

Preparation of N-[(4'-dimethylamino-2'-methoxy)phenyl]-2,6-dimethyl-3-acetylamino benzoquinoneimine. ##SPC39##

0.01 mole (2.64 g) of 3-methoxy-4-amino-N,N-dimethylaniline sulfate and0.01 mole (1.8 g) of 2,6-dimethyl-5-acetylamino phenol are dissolved in25 cc of acetone, 50 cc of water and 15 cc of ammonia (22°Be). To theresulting solution, maintained at a temperature of about 0°C., there isadded, little by little, with agitation, 0.02 mole (4.6 g) of ammoniumpersulfate dissolved in 20 cc of water. At the end of this addition, thestirring of the reaction mixture is continued for 30 minutes. The aboveindoaniline which has precipitated is then filtered, washed first withwater, then with a little dimethylformamide and finally with water.After drying under a vacuum, the product exhibits a melting point of186°C.

    ______________________________________                                                     Calculated For                                                   Analysis     C.sub.19 H.sub.23 N.sub.3 O.sub.3                                                                Found                                         ______________________________________                                        C%           66.84              66.64                                         H%            6.79               6.70                                         N%           12.31              12.42                                         ______________________________________                                    

EXAMPLE XXXI

Preparation of N-[(4'-dimethylamino-2'-chloro)phenyl]-6-methyl-3-(β-hydroxyethylamino) benzoquinoneimine. ##SPC40##

0.01 mole (1.67 g) of 2-methyl-5-(N-β-hydroxy-ethylamino) phenol isdissolved in 10 cc of acetone, 5 cc of water and 15 cc of ammonia(22°Be). To the resulting solution, maintained at a temperature of about+5°C., there are added, little by little, with agitation andsimultaneously with the aid of a double funnel, 0.01 mole (2.43 g) ofthe dihydrochloride of 3-chloro-4-amino-N,N-diemthylaniline dissolved in15 cc of water, and 0.01 mole (2.3 g) of ammonium persulfate dissolvedin 10 cc of water. At the end of these additions, the stirring of thereaction mixture is continued for 30 minutes. The above indoanilinewhich has precipitated in the form of crystals is then filtered, washedwith water, recrystallized in a mixture of dimethylformamide and waterand dried under a vacuum. It exhibits a melting point of 176°C.

    ______________________________________                                                     Calculated For                                                   Analysis     C.sub.17 H.sub.20 N.sub.3 O.sub.2 Cl                                                             Found                                         ______________________________________                                        C%           61.17              60.94                                         H%            5.99               6.10                                         N%           12.60              12.51                                         Cl%          10.65              10.60                                         ______________________________________                                    

EXAMPLE XXXII

Preparation of N-[(4'-diethylamino-3'-methyl)phenyl]-6-methyl-3-acetylamino benzoquinoneimine. ##SPC41##

0.0064 mole (1.06 g) of 2-methyl-5-acetylamino phenol and 0.0064 (1.65g) of 2-methyl-4-amino-N,N-diethylaniline are dissolved in 80 cc of a50% hydroacetonic solution to which have been added 20 cc of ammonia(22°Be). To the resulting solution, cooled to 0°C., there is added,little by little, with a little agitation, 0.0128 mole (2.9 g) ofammonium persulfate dissolved in 20 cc of water. The resulting reactionmixture is left to stand overnight at 0°C. The above indoaniline whichforms first as an oil, crystallizes and the resulting crystals arefiltered, washed with water and recrystallized in a mixture ofdimethylformamide and water. After drying under a vacuum the productexhibits a melting point of 84°C.

    ______________________________________                                                   Calculated For                                                     Analysis   C.sub.20 H.sub.25 N.sub.3 O.sub.2.O.5H.sub.2 O                                                     Found                                         ______________________________________                                        C%         68.94                68.97                                         H%          7.52                 7.42                                         N%         12.06                11.98                                         ______________________________________                                    

EXAMPLE XXXIII

Preparation of N-[(4'-dimethylamino-3'-chloro) phenyl]-2,6-dimethylbenzoquinoneimine. ##SPC42##

0.01 mole (1.22 g) of 2,6-dimethyl phenol and 0.01 mole (1.70 g) of2-chloro-4-amino-N,N-dimethyl aniline are dissolved in 30 cc of a 50%hydroacetonic solution to which have been added 15 cc of ammonia(22°Be). To the resulting solution, maintained at a temperature of 0°C.,there is added, little by little, with agitation 0.02 mole (4.6 g) ofammonium persulfate dissolved in 20 cc of water. At the end of thisaddition, the stirring of the reaction mixture is continued for 30minutes. The above indoaniline which has precipitated in the form ofcrystals is then filtered, washed with water and recrystallized in amixture of dimethylformamide and water and dried under a vacuum. Itexhibits a melting point of 62°C.

    ______________________________________                                                     Calculated For                                                   Analysis     C.sub.16 H.sub.17 ClN.sub.2 O                                                                    Found                                         ______________________________________                                        C%           66.19              66.39                                         H%           5.58               5.73                                          N%           9.70               9.87                                          Cl%          12.27              12.47                                         ______________________________________                                    

EXAMPLE XXXIV

Preparation of N-[(4'-dimethylamino-3'-chloro) phenyl]-6-methyl-3-aminobenzoquinoneimine. ##SPC43##

0.004 mole (1.33 g) of N-[(4'-dimethylamino-3'-chloro)phenyl]-6-methyl-3-acetylamino benzoquinoneimine is introduced into 32cc of a 1N NaOH solution to which have been added 8 cc of ethylalcohol(95°titer). The resulting reaction mixture is agitated for a period of24 hours while maintaining the temperature thereof at about 25°C. Theabove indoaniline which precipitates is then filtered and washed withwater. The raw product contains only a trace of the initial reactant(measured by chromatography). After recrystallization of this rawproduct in a mixture of dimethylformamide and water and washing withacetone it is chromatographically pure. After drying under a vacuum, itexhibits a melting point of 152°C.

    ______________________________________                                                     Calculated For                                                   Analysis     C.sub.15 H.sub.16 ClN.sub.3 O                                                                    Found                                         ______________________________________                                        C%           62.16              62.38                                         H%            5.56               5.36                                         N%           14.50              14.57                                         Cl%          12.23              12.13                                         ______________________________________                                    

EXAMPLE XXXV

Preparation of N-[(4'-dimethylamino-3'-chloro) phenyl]-6-chloro-3-aminobenzoquinoneimine. ##SPC44##

0.01 mole (1.70 g) of 2-chloro-4-amino-N,N-dimethylaniline and 0.01 mole(1.43 g) of 2-chloro-5-amino phenol are dissolved in 20 cc of water, 30cc of ethylalcohol (95°titer) and 10 cc of ammonia (22°Be). To theresulting solution, maintained at a temperature of about 0°C., there isadded, little by little, with agitation, 0.01 mole (2.3 g) of ammoniumpersulfate dissolved in 20 cc of water. At the end of this addition, thestirring of the reaction mixture is continued for 30 minutes. The aboveindoaniline which has precipitated in the form of reddish brown flakeswith golden glints is then filtered, washed with water andrecrystallized in a mixture of dimethylformamide and water. After dryingunder a vacuum at 100°C., the produce exhibits a melting point of 182°C.

    ______________________________________                                                     Calculated For                                                   Analysis     C.sub.14 H.sub.13 N.sub.3 Cl.sub.2 O                                                             Found                                         ______________________________________                                        C%           54.19              54.19                                         H%            4.19               4.30                                         N%           13.54              13.66                                         Cl%          22.90              23.12                                         ______________________________________                                    

EXAMPLE XXXVI

Preparation of N-](4'-dimethylamino-3'-chloro)phenyl]-2,6-dimethyl-3-amino benzoquinoneimine ##SPC45##

0.02 mole (3.47 g) of the hydrochloride of 2,6-dimethyl-5-amino phenoland 0.02 mole (3.42 g) of 2-chloro-4-amino-N,N-dimethylaniline aredissolved in 120 cc of a 50% hydroacetonic solution to which have beenadded 30 cc of ammonia (22°Be). To the resulting solution, maintained ata temperature of 0°C., there is added, little by little, with agitation0.04 mole (9.2 g) of ammonium persulfate dissolved in 40 cc of water. Atthe end of this addition, the stirring of the reaction mixture iscontinued for 30 minutes at 0°C. The above indoaniline whichprecipitates is then filtered, washed with water and recrystallized in amixture of dimethylformamide and water. After drying under a vacuum at60°C., it exhibits a melting point of 137°C.

    ______________________________________                                                   Calculated For                                                     Analysis   C.sub.16 H.sub.18 N.sub.3 OCl.O.5H.sub.2 O                                                         Found                                         ______________________________________                                        C%         61.44                61.25                                         H%          6.08                 6.16                                         N%         13.44                13.24                                         Cl%        11.36                11.31                                         ______________________________________                                    

EXAMPLE XXXVII

Preparation of N-[(4'-dimethylamino-3'-chloro)phenyl]-6-methyl-3-acetylamino benzoquinoneimine ##SPC46##

0.01 mole (1.65 g.) of 2-methyl-5-acetylamino phenol and 0.01 mole (1.71g) of 2-chloro-4-amino-N,N-dimethylaniline are dissolved in 60 cc of a50% hydroacetonic solution to which have been added 15 cc of ammonia(22° Be). To the resulting solution, maintained at a temperature ofabout 0° C., there is added, little by little, with agitation, 0.02 mole(4.6 g) of ammonium persulfate dissolved in 20 cc of water. At the endof this addition, the stirring of the reaction mixture is continued for30 minutes. The above indoaniline which has precipitated in the form ofcrystals is then filtered, washed with water, recrystallized in amixture of dimethylformamide and water and dried under a vacuum. Itexhibits a melting point of 156°C.

    ______________________________________                                                   Calculated For                                                     Analysis   C.sub.17 H.sub.18 O.sub.2 N.sub.3 Cl.O.5H.sub.2 O                                                  Found                                         ______________________________________                                        C%         59.91                59.87                                         H%          5.62                 5.60                                         N%         12.33                12.58                                         Cl%        10.40                10.52                                         ______________________________________                                    

EXAMPLE XXXVIII

Preparation of N-[(4'-dimethylamino-3'-chloro)phenyl]-2,6-dimethyl-3-acetylamino benzoquinoneimine. ##SPC47##

0.2 mole (35.8 g) of 2,6-dimethyl-5-acetylamino phenol and 0.2 mole(34.0 g) of 2-chloro-4-amino-N,N-dimethylaniline are dissolved in 600 ccof a 50% hydroacetonic solution to which have been added 300 cc ofammonia (22° Be). To the resulting solution, maintained at a temperatureof about -5°C., there is added, little by little, with agitation, 0.4mole (92 g) of ammonium persulfate dissolved in 400 cc of water. At theend of this addition, the stirring of the reaction mixture is continuedfor 30 minutes. The above indoaniline which has precipitated is thenfiltered, washed with water, recrystallized in a mixture ofdimethylformamide and water and dried under a vacuum. It exhibits amelting point of 136°C.

    ______________________________________                                                     Calculated For                                                   Analysis     C.sub.18 H.sub.20 ClN.sub.3 O.sub.2                                                              Found                                         ______________________________________                                        C%           62.52              62.54                                         H%            5.82               5.95                                         N%           12.15              12.24                                         Cl%          10.25              10.42                                         ______________________________________                                    

EXAMPLE XXXIX

Preparation of N-[(4'-dimethylamino-3'-chloro]phenyl]-6-methyl-3-carbethoxyamino benzoquinoneimine. ##SPC48##

0.1 mole (17 g) of 2-chloro-4-amino-N,N-dimethylaniline and 0.1 mole(19.5 g) of 2-methyl-5-carbethoxyamino phenol are dissolved in 500 cc ofethyl alcohol (95° titer), 250 cc of water and 150 cc of ammonia (22°Be). To the resulting solution maintained at a temperature of about0°C., there is added, little by little, with agitation, 0.2 mole (46 g)of ammonium persulfate dissolved in 200 cc of water. At the end of thisaddition, the stirring of the reaction mixture is continued for onehour. The above indoaniline which has precipitated in the form ofcrystals is then filtered and washed with a 50% hydroethanolic solution.After recrystallization in a mixture of dimethylformamide and water anddrying under a vacuum at 100°C., the product exhibits a melting point of142°C.

    ______________________________________                                                     Calculated For                                                   Analysis     C.sub.18 H.sub.20 N.sub.3 O.sub.3 Cl                                                             Found                                         ______________________________________                                        C%           59.75              59.81                                         H%            5.54               5.69                                         N%           11.62              11.55                                         Cl%           9.82               9.89                                         ______________________________________                                    

EXAMPLES OF USE Section A Examples of Hair Setting Lotions

    ______________________________________                                        (a)     Dye according to Example IV                                                                           0.02 g                                                Copolymer of vinyl acetate and                                                crotonic acid 90/10; molecular                                                weight 45,000 to 50,000 1 g                                                   Isopropyl alcohol       20 g                                                  Triethanolamine q.s.p. pH 6.5                                                 Water q.s.p.            100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a purple-ash shade.

    ______________________________________                                        (b)   Dye according to Example VI                                                                              0.15 g                                             Terpolymer of methylmethacrylate/                                             stearylmethacrylate/dimethylmethacrylate,                                     20/23/57 (made in accordance with SN 287,845                                  filed 11-9-1972)           2.5 g                                              Ethyl alcohol (96°) 30 g                                               Triethanolamine q.s.p. pH 7.5                                                 Water q.s.p.               100 g                                        ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a silvery, blue-gray coloration.

    ______________________________________                                        (c)    Dye according to Example VIII                                                                          0.1 g                                                Polyvinylpyrrolidone - M.W. 40,000                                                                     2 g                                                  Isopropyl alcohol        35 g                                                 Triethanolamine q.s.p. pH 9                                                   Water q.s.p.             100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a chayoyant sea-green coloration.

    ______________________________________                                        (d)  Dye according to Example V 0.15 g                                             Copolymer of vinyl acetate/                                                   crotonic acid 90/10, M.W. 45,000                                              to 50,000                  1.5 g                                              Ethyl alcohol (96°) 30 g                                               Triethanolamine q.s.p. pH 6.2                                                 Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a bright blue-green coloration.

    ______________________________________                                        (e)  Dye according to Example XI                                                                              0.12 g                                             Polyvinylpyrrolidone, M.W. 40,000                                                                        1 g                                                Ethyl alcohol (96°) 20 g                                               Triethanolamine q.s.p. pH 10.2                                                Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a Nordic ash-blond coloration.

    ______________________________________                                        (f)  N-[(4'-dimethylamino) phenyl]-3-                                              acetylamino benzoquinoneimine                                                                            0.2 g                                              polyvinylpyrrolidone/vinyl, acetate                                           70/30, M.W. 40,000         3 g                                                Ethyl alcohol (96°) 45 g                                               Triethanolamine q.s.p. pH 7.8                                                 Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a silvery Prussian blue coloration.

    ______________________________________                                        (g)  Dye according to Example X 0.04 g                                             Terpolymer of methylmethacrylate/                                             stearylmethacrylate/dimethyl-                                                 methacrylate, 20/23/57 (made in accordance                                    with SN 287,845 filed 11-9-1972)                                                                         3 g                                                Ethyl alcohol (96°) 50 g                                               Triethanolamine q.s.p. pH 8.2                                                 Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a pale glycine coloration.

    ______________________________________                                        (h)  N-[(4'-dimethylamino) phenyl]-                                                2,6-tert. butyl benzoquinone-                                                 imine                      0.05 g                                             Polyvinylpyrrolidone, M.W. 40,000                                                                        3 g                                                Isopropyl alcohol          50 g                                               Triethanolamine q.s.p. pH 6                                                   Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a mauve shade.

    ______________________________________                                        (i)  N-[(4'-dimethylamino) phenyl]-                                                3-methoxy benzoquinoneimine                                                                              0.1 g                                              Polyvinylpyrrolidone, M.W. 40,000                                                                        1.5 g                                              Ethyl alcohol (96°) 30 g                                               Triethanolamine q.s.p. pH 6                                                   Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a light lavender-blue color.

    ______________________________________                                        (j)  Dye according to Example I 0.08 g                                             Copolymer of vinylpyrrolidone/                                                vinyl acetate, 60/40 M.W. 80,000-120,000                                                                 2 g                                                Ethyl alcohol (96°) 25 g                                               Triethanolamine q.s.p. pH 8.7                                                 Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a pale shade with golden glints.

    ______________________________________                                        (k)  N-[(4'-dimethylamino) phenyl]                                                 benzoquinoneimine          0.12 g                                             Copolymer of vinylpyrrolidone/                                                vinyl acetate, 60/40, M.W. 80,000-120,000                                                                2.5 g                                              Isopropyl alcohol          40 g                                               Triethanolamine q.s.p. pH 7.5                                                 Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a pale-green coloration with golden glints.

    ______________________________________                                        (l)  Dye according to Example IX                                                                              0.05 g                                             Copolymer of vinylpyrrolidone/                                                vinyl acetate, 70/30, M.W. 40,000                                                                        1 g                                                Ethyl alcohol (96°) 50 g                                               Triethanolamine q.s.p. pH 6.8                                                 Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a bright sea-green coloration.

    ______________________________________                                        (m)  Dye according to Example VII                                                                             0.05 g                                             Copolymer of vinylpyrrolidone/                                                vinyl acetate, 70/30, M.W. 40,000                                                                        2 g                                                Isopropyl alcohol          45 g                                               Triethanolamine q.s.p. pH 8.5                                                 Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a pearly, pale rose shade.

    ______________________________________                                        (n)  Dye according to Example II                                                                              0.1 g                                              Copolymer of vinylpyrrolidone/                                                vinyl acetate, 30/70, M.W. 160,000                                                                       3 g                                                Isopropyl alcohol          50 g                                               Triethanolamine q.s.p. pH 9                                                   Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a steel, blue-gray coloration.

    ______________________________________                                        (o)  N-[(4'-dimethylamino) phenyl]-                                                2,5-dimethyl benzoquinoneimine                                                                           0.15 g                                             Copolymer of vinyl acetate/                                                   crotonic acid 90/10, M.W. 45,000                                              to 50,000                  1 g                                                Ethyl alcohol (96°) 40 g                                               Triethanolamine q.s.p. pH 10                                                  Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a steel, blue-gray coloration.

    ______________________________________                                        (p)  Dye according to Example III                                                                              0.08 g                                            Copolymer of vinyl acetate/crotonic                                           acid 90/10, M.W. 45,000-50,000                                                                            1 g                                               Ethyl alcohol               50 g                                              Triethanolamine q.s.p. pH 9.5                                                 Water q.s.p.                100 g                                        ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto an ash-gray coloration.

    ______________________________________                                        (q)  N-[(4'-dimethylamino) phenyl]-                                                2,6-dimethyl benzoquinoneimine                                                                           0.05 g                                             Polyvinylpyrrolidone, M.W. 40,000                                                                        3 g                                                Isopropyl alcohol          40 g                                               Triethanolamine q.s.p. pH 10.2                                                Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a silvery, blue-green coloration.

    ______________________________________                                        (r)  Dye according to Example XII                                                                             0.08 g                                             Copolymer of vinylpyrrolidone/                                                vinyl acetate, 30/70, M.W. 160,000                                                                       1.5 g                                              Ethyl alcohol (96°) 25 g                                               Triethanolamine q.s.p. pH 7.5                                                 Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a pearly beige coloration.

    ______________________________________                                        (s)  Dye according to Example XIII                                                                            0.09 g                                             Copolymer of vinylpyrrolidone/                                                vinyl acetate, 70/30, M.W. 40,000                                                                        1.5 g                                              Ethyl alcohol (96°) 50 g                                               Triethanolamine q.s.p. pH 8.5                                                 Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto, a rose-gray coloration.

    ______________________________________                                        (t)  Dye according to Example XIV                                                                             0.52 g                                             Copolymer of vinyl acetate/                                                   crotonic acid 90/10, M.W. 45,000-                                             50,000                     2 g                                                Ethanol (96°)       50 g                                               Water q.s.p.               100 g                                              Triethanolamine q.s.p. pH 7                                              ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto, a light silvery-gray coloration.

    ______________________________________                                        (u)  Dye according to Example XV                                                                              0.04 g                                             Copolymer of vinylpyrrolidone/                                                vinyl acetate, 30/70, M.W. 60,000                                                                        2 g                                                Ethyl alcohol (96°) 40 g                                               Triethanolamine, q.s.p. pH 9                                                  Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a light pearly blue coloration.

    ______________________________________                                        (v)  Dye according to Example XVI                                                                             0.2 g                                              Copolymer of vinylpyrrolidone/                                                vinyl acetate, 30/70, M.W. 60,000                                                                        2 g                                                Ethyl alcohol (96°) 40 g                                               Triethanolamine, q.s.p. pH 7                                                  Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a lightly violaceous blue coloration.

    ______________________________________                                        (w)  Dye according to Example XVII                                                                            0.0075 g                                           Copolymer of vinylpyrrolidone/                                                vinyl acetate, 60/40, sold under                                              the name of PVP/VA S630    2 g                                                Isopropanol                35 g                                               Triethanolamine q.s.p. pH 7.5                                                 Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a light pearly turquoise blue coloration.

    ______________________________________                                        (x)  Dye according to Example XVIII                                                                           0.25 g                                             Copolymer of vinyl acetate/                                                   crotonic acid, 90/10, M.W. - 45,000                                           to 50,000                  2 g                                                Ethyl alcohol (96°) 50 g                                               Triethanolamine q.s.p. pH 7                                                   Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto an intense violet coloration.

    ______________________________________                                        (y)  Dye according to Example XIX                                                                             0.6 g                                              Copolymer of vinyl acetate/                                                   crotonic acid, 90/10, M.W. -                                                  45,000 to 50,000           1 g                                                Ethyl alcohol (96°) 36 g                                               Triethanolamine q.s.p. pH 9                                                   Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a very luminous parme coloration.

    ______________________________________                                        (z)  Dye according to Example XX                                                                              0.26 g                                             Copolymer of vinyl acetate/                                                   crotonic acid, 90/10, M.W. -                                                  45,000 to 50,000           2 g                                                Ethyl alcohol (96°) 50 g                                               Lactic acid - 10% solution,-                                                                             q.s.p. pH 4.5                                      Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a very silvery light violet coloration.

    ______________________________________                                        (aa) Dye of Example XXI         0.1 g                                              Copolymer of vinylpyrrolidone/                                                vinyl acetate, 30/70, sold under                                              the name PVP/VAE E335      2 g                                                Ethyl alcohol (96°) 40 g                                               Ammonia (22°Be), q.s.p. pH 6                                           Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applield as a hair setting lotion to bleached hairimparts thereto a pearly rose beige coloration.

    ______________________________________                                        (ab) Dye of Example XXII        0.15 g                                             Copolymer of vinylpyrrolidone/                                                vinyl acetate, 60/40, sold under                                              the name PVP/VA S630       2 g                                                Isopropanol                35 g                                               Triethanolamine, q.s.p. pH 9.5                                                Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a pearly light blue coloration.

    ______________________________________                                        (ac) Dye of Example XXIII       0.1 g                                              Copolymer of vinylpyrrolidone/                                                vinyl acetate, 60/40, sold under                                              the name PVP/VA S630       2 g                                                Isopropanol                35 g                                               Triethanolamine q.s.p. pH 8.5                                                 Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a light blue coloration.

    ______________________________________                                        (ad) Dye of Example XXIV        0.05 g                                             Copolymer of vinylpyrrolidone/                                                vinyl acetate, 30/70, sold under                                              the name PVP/VAE E335      2 g                                                Ethyl alcohol (96°) 40 g                                               Lactic acid - 10% solution,                                                   q.s.p. pH 5                                                                   Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a silvery light blue-gray coloration.

    ______________________________________                                        (ae) Dye of Example XXV         0.15 g                                             Copolymer of vinyl acetate/                                                   crotonic acid, 90/10, M.W. -                                                  45,000 to 50,000           1 g                                                Ethyl alcohol (96°) 36 g                                               Lactic acid - 10% solution,                                                   q.s.p. pH 5                                                                   Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a silvery glycine coloration.

    ______________________________________                                        (af) Dye of Example XXVI        0.05 g                                             Copolymer of vinyl acetate/                                                   crotonic acid, 90/10, M.W. -                                                  45,000 to 50,000           2 g                                                Ethyl alcohol (96°) 50 g                                               Triethanolamine q.s.p. pH 5                                                   Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a golden-rose coloration.

    ______________________________________                                        (ag) Dye of Example XXVII       0.12 g                                             Copolymer of vinylpyrrolidone/                                                vinyl acetate, 30/70, sold under                                              the name PVP/VAE E335      2 g                                                Ethyl alcohol (96°) 40 g                                               Ammonia (22°Be), q.s.p. pH 9                                           Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a very luminous parme coloration.

    ______________________________________                                        (ah) Dye of Example XXVIII      0.12 g                                             Copolymer of vinylpyrrolidone/                                                vinyl acetate, 60/40, sold under                                              the name PVP/VA S630       2 g                                                Isopropanol                35 g                                               Ammonia (22°Be), q.s.p. pH 9                                           Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a myosotis coloration.

    ______________________________________                                        (ai) Dye of Example XXIX        0.05 g                                             Copolymer of vinyl acetate/                                                   crotonic acid, 90/10, M.W. -                                                  45,000 to 50,000           2 g                                                Ethyl alcohol (96°) 50 g                                               Ammonia (22°Be) q.s.p. pH 8.5                                          Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a silver-gray coloration with violet glints.

    ______________________________________                                        (aj) Dye of Example XXX         0.2 g                                              Copolymer of vinylpyrrolidone/                                                vinyl acetate, 60/40, sold under                                              the name PVP/VA S630       2 g                                                Isopropanol                35 g                                               Lactic acid - 10% solution,                                                   q.s.p. pH 5                                                                   Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a intense French blue coloration.

    ______________________________________                                        (ak) Dye of Example XXXI        0.05 g                                             Copolymer of vinyl acetate/                                                   crotonic acid, 90/10, M.W. -                                                  45,000 to 50,000           2 g                                                Ethyl alcohol (96°) 50 g                                               Triethanolamine q.s.p. pH 6                                                   Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a pearly dog-rose coloration.

    ______________________________________                                        (al) Dye of Example XXXI        0.25 g                                             N-[(4'-hydroxy-3'-chloro) phenyl]-                                            2-methyl-5-β-hyd oxyethylamino                                           benzoquinoneimine          0.25 g                                             Copolymer of vinyl acetate/                                                   crotonic acid, 90/10, M.W. -                                                  45,000 to 50,000           2 g                                                Ethyl alcohol (96°) 36 g                                               Ammonia (22°Be) q.s.p. pH 8                                            Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a rose beige coloration with golden glints.

    ______________________________________                                        (am) Dye of Example XIX         0.12 g                                             Dye of Example XVII        0.05 g                                             N-[(4'-hydroxy-3'-chloro) phenyl]-2,                                          6-dimethyl-5-amino benzoquinoneimine                                                                     0.35 g                                             Nitroorthophenylenediamine 0.02 g                                             Terpolymer of methylmethacrylate/                                             stearylmethacrylate/dimethyl-                                                 methacrylate, 20/23/57 (made in accordance                                                               1.25 g                                             with SN 287,845 filed 11-9-1972)                                              Ethyl alcohol (96°) 15 g                                               Ammonia (22°Be) q.s.p. pH 9                                            Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto an ash gray coloration.

    ______________________________________                                        (an) Dye of Example XVIII       0.2 g                                              N-[(4'-hydroxy) phenyl]-2-methyl-                                             5-β-hydroxyethylamino benzo-                                             quinoneimine               0.30 g                                             N-[(4'-hydroxy) phenyl]-2-methyl-                                             5-carbethoxyamino benzoquinone-                                               imine                      0.20 g                                             Polyvinylpyrrolidone, M.W. 160,000                                                                       2 g                                                Isopropanol                25 g                                               Ammonia (22°Be) q.s.p. pH 9.7                                          Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a mahogany coloration.

    ______________________________________                                        (ao) Dye of Example XXXII       0.5 g                                              Copolymer of vinyl acetate/                                                   crotonic acid, 90/10, M.W. -                                                  45,000 to 50,000           2 g                                                Ethyl alcohol (96°) 50 g                                               Lactic acid - 10% solution,                                                   q.s.p. pH 5                                                                   Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a tamarisk rose coloration.

    ______________________________________                                        (ap) Dye of Example XXXIII      0.025 g                                            Copolymer of vinyl acetate/                                                   crotonic acid, 90/10, M.W. -                                                  45,000 to 50,000           2 g                                                Ethyl alcohol (96°) 50 g                                               Triethanolamine q.s.p. pH 7.5                                                 Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a pink champagne coloration.

    ______________________________________                                        (aq) Dye of Example XXXIV       0.040 g                                            Copolymer of vinyl acetate/                                                   crotonic acid, 90/10, M.W. -                                                  45,000 to 50,000           2 g                                                Ethyl alcohol (96°) 50 g                                               Triethanolamine q.s.p. pH 7                                                   Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a light yellow-orange coloration.

    ______________________________________                                        (ar) Dye of Example XXXV        0.08 g                                             Polyvinylpyrrolidone, M.W. 160,000                                                                       1.5 g                                              Ethyl alcohol (96°) 50 g                                               Ammonia (22°Be) q.s.p. pH 10                                           Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a pearly rose beige coloration.

    ______________________________________                                        (as) Dye of Example XXXVI       0.2 g                                              Copolymer of vinyl acetate/                                                   crotonic acid, 90/10, M.W. -                                                  45,000 to 50,000           1 g                                                Ethyl alcohol (96°) 36 g                                               Ammonia (22°Be) q.s.p. pH 6                                            Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a light orange coloration.

    ______________________________________                                        (at) Dye of Example XXXVII      0.1 g                                              Copolymer of vinyl acetate/                                                   crotonic acid, 90/10, M.W. -                                                  45,000 to 50,000           2 g                                                Ethyl alcohol (96°) 50 g                                               Triethanolamine q.s.p. pH 7                                                   Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a very luminous light salmon coloration.

    ______________________________________                                        (au) Dye of Example XXXVIII     0.5 g                                              Copolymer of vinylpyrrolidone/                                                vinyl acetate, 30/70, sold under                                              the name PVP/VAE E335      2 g                                                Ethyl alcohol (96°) 40 g                                               Triethanolamine q.s.p. pH 9                                                   Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a salmon rose coloration.

    ______________________________________                                        (av) Dye of Example XXXIX       0.075 g                                            Copolymer of vinylpyrrolidone/                                                vinyl acetate, 30/70, sold under                                              the name PVP/VAE E335      2 g                                                Ethyl alcohol (96°) 40 g                                               Lactic acid - 10% solution,                                                   q.s.p. pH 5                                                                   Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto a golden sand coloration with light pink glints.

    ______________________________________                                        (aw) Dye of Example XXXVII      0.10 g                                             Dye of Example XXXVI       0.12 g                                             N-[(4'-amino-2'-methoxy-3',5'-                                                dimethyl) phenyl]-2,6-dimethyl-                                               3-acetylamino benzoquinoneimine                                                                          0.05 g                                             2-N,N-(methyl,β-hydroxyethyl)amino-5-                                    (4'-amino) anilino-1,4-benzoquinone                                                                      0.08 g                                             Copolymer of vinyl acetate/                                                   crotonic acid, 90/10, M.W. -                                                  45,000 to 50,000           2 g                                                Ethyl alcohol (96°) 50 g                                               Ammonia (22°Be) q.s.p. pH 10                                           Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to bleached hairimparts thereto an ash beige coloration.

    ______________________________________                                        (ax) Dye of Example XXXVI       0.20 g                                             N-[(4'-amino-2'-methoxy-3'-5'-                                                dimethyl) phenyl]-2,6-dimethyl-                                               3-acetylamino benoquinoneimine                                                                           0.04 g                                             N-[(4'-(ethyl,β-mesylaminoethyl)                                         amino-2'-methyl) phenyl]-2,3-                                                 dimethyl benzoquinoneimine 0.25 g                                             Copolymer of vinyl acetate/                                                   crotonic acid, 90/10, M.W. -                                                  45,000 to 50,000           2 g                                                Ethanol (95°)       50 g                                               Triethanolamine q.s.p. pH 6                                                   Water q.s.p.               100 g                                         ______________________________________                                    

This composition when applied as a hair setting lotion to 95% naturallywhite hair, imparts thereto a metallic gray coloration with violetglints.

Section B Examples of Dye Compositions

    ______________________________________                                        (a)  N-[(4'-dimethylamino) phenyl]-3-                                              acetylamino benzoquinoneimine                                                                            0.3 g                                              Ammonium lauryl sulfate    20 g                                               Triethanolamine q.s.p. pH 8.5                                                 Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied for a period of 30 minutes to white hairat ambient temperature. The hair is then rinsed, shampooed, rinsed againand then dried. A pearly sea-green coloration is thus imparted to thehair.

    ______________________________________                                        (b)  Dye according to Example V 0.2 g                                              Ammonium lauryl sulfate    20 g                                               Triethanolamine q.s.p. pH 9                                                   Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied for a period of 30 minutes to white hairat ambient temperature. The hair is then rinsed, shampooed, rinsed againand dried. A sea-green coloration is thus imparted to the hair.

    ______________________________________                                        (c)  Dye according to Example VI                                                                              0.3 g                                              Butylglycol                5 g                                                Lauryl alcohol oxyethylenated with                                            10.5 moles of ethylene oxide                                                                             5 g                                                Triethanolamine q.s.p. pH 9                                                   Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied to white hair for a period of 30 minutesat ambient temperature. After rinsing, shampooing, rinsing again anddrying, a lavender-blue coloration is imparted to the hair.

    ______________________________________                                        (d)  N-[(4'-dimethylamino) phenyl]-3-                                              acetylamino benzoquinoneimine                                                                            0.3 g                                              Ethanol (96°)       30 g                                               Acetic acid q.s.p. pH 5                                                       Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied for about 30 minutes to previouslybleached hair. At the end of this period, the hair is rinsed and dried.A brilliant turquoise coloration is thus imparted to the hair.

    ______________________________________                                        (e)  Dye of Example XVII        0.15 g                                             Diethanolamides of the fatty                                                  acids of copra             10 g                                               Phosphoric acid - 10% solution,                                               q.s.p. pH 4                                                                   Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied for a period of 20 minutes at 35°C., tobleached hair and after rinsing, shampooing, and rinsing again impartsthereto a turquoise blue coloration.

    ______________________________________                                        (f)  Dye of Example XIX         2 g                                                Diethanolamides of fatty                                                      acids of copra             10 g                                               Ammonia (22°Be) q.s.p. pH 10                                           Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied for a period of 25 minutes to 90%naturally white hair at 35°C., and after rinsing, shampooing and rinsingagain imparts thereto a blue gray coloration.

    ______________________________________                                        (g)  Dye of Example XX          0.3 g                                              Sodium lauryl sulfate with 19%                                                of the starting alcohol being                                                 oxyethylenated             20 g                                               Ethylenediamine tetraacetic acid-                                             "TRILON B"                 0.2 g                                              Ammonia (22°Be) q.s.p. pH 11                                           Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied for a period of 20 minutes at 30°C., tobleached hair and after rinsing, shampooing and rinsing again, impartsthereto a light silver coloration with mauve glints.

    ______________________________________                                        (h)  Dye of Example XXI         0.2 g                                              Monomethyl ester of diethylene                                                glycol                     10 g                                               Ammonia (22°Be) q.s.p. pH 9                                            Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied for a period of 30 minutes at 25°C., tobleached hair and after rinsing, shampooing and rinsing again impartsthereto a golden rose coloration.

    ______________________________________                                        (i)  Dye of Example XXIII       0.1 g                                              Ammonium lauryl sulfate    10 g                                               acetic acid - 5% solution,                                                    q.s.p. pH 7                                                                   Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied for a period of 25 minutes at 35°C., tobleached hair and after rinsing, shampooing and rinsing again, impartsthereto a pearly light turquoise coloration.

    ______________________________________                                        (j)  Dye of Example XXIV        0.25 g                                             Carboxymethyl cellulose    5 g                                                Ammonia (22°Be) q.s.p. pH 11                                           Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied for a period of 25 minutes at 35°C., tobleached hair and after rinsing, shampooing and rinsing again, impartsthereto a light silver coloration with bluish glints.

    ______________________________________                                        (k)  Dye of Example XXVII       0.3 g                                              Butylglycol                5 g                                                Lauryl alcohol oxyethylenated                                                 with 10.5 moles of ethylene                                                   oxide                      5 g                                                Ammonia (22°Be) q.s.p. pH 10                                           Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied for a period of 25 minutes at 35°C., to95% naturally white hair and after rinsing, shampooing and rinsingagain, imparts thereto a silver gray coloration with mauve glints.

    ______________________________________                                        (l)  Dye of Example XXX         0.20 g                                             Carboxymethyl cellulose    5 g                                                Ammonia (22°Be) q.s.p. pH 8                                            Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied for a period of 25 minutes at 20°C., tobleached hair and after rinsing, shampooing and rinsing again, impartsthereto a silvery light blue coloration.

    ______________________________________                                        (m)  Dye of Example XXVII       0.30 g                                             N-[(4'-hydroxy-2'-chloro)-phenyl]-                                            2-methyl-5-amino benzoquinoneimine                                                                       0.40 g                                             Ethyl alcohol (96°) 20 g                                               Diethanolamides of fatty acids                                                of copra                   8 g                                                Ammonia (22°Be) q.s.p. pH 9.3                                          Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied for a period of 20 minutes at ambienttemperature to bleached hair and after rinsing, shampooing and rinsingagain, imparts thereto a light golden blond coloration with pink glints.

    ______________________________________                                        (n)  Dye of Example XXXIII      0.75 g                                             Butylglycol                5 g                                                Lauryl alcohol oxyethylenated                                                 with 10.5 moles of ethylene oxide                                                                        5 g                                                Ammonia (22°Be) q.s.p. pH 10.5                                         Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied for a period of 20 minutes at ambienttemperature to bleached hair and after rinsing, shampooing and rinsingagain, imparts thereto a pale golden pink coloration.

    ______________________________________                                        (o)  Dye of Example XXXVI       0.1 g                                              Lauryl alcohol oxyethylenated                                                 with 10.5 moles of ethylene oxide                                                                        5 g                                                Ammonia (22°Be) q.s.p. pH 10                                           Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied for a period of 20 minutes at 35°C., tobleached hair and after ringins, shampooing and rinsing again, impartsthereto a very luminous orange coloration.

    ______________________________________                                        (p)  Dye of Example XXXVII      0.1 g                                              Monomethyl ester of diethylene                                                glycol                     10 g                                               Ammonia (22°Be) q.s.p. pH 11                                           Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied for a period of 25 minutes at 35°C., tobleached hair and after rinsing, shampooing and rinsing again, impartsthereto a pink beige coloration.

    ______________________________________                                        (q)  Dye of Example XXXVIII     0.25 g                                             Ethyl alcohol (96°) 20 g                                               Carboxymethyl cellulose    5 g                                                Lactic acid - 10% solution,                                                   q.s.p. pH 5                                                                   Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied for a period of 10 minutes at 35°C., tobleached hair and after rinsing, shampooing and rinsing again, impartsthereto a tamarisk-pink coloration.

    ______________________________________                                        (r)  Dye of Example XXXIV       0.425 g                                            Butylglycol                5 g                                                Lauryl alcohol oxyethylenated                                                 with 10.5 moles of ethylene oxide                                                                        5 g                                                Ammonia (22°Be) q.s.p. pH 9                                            Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied for a period of 20 minutes at ambienttemperature to bleached hair and imparts thereto a pearly golden sandcoloration.

    ______________________________________                                        (s)  Dye of example XXXIII      0.40 g                                             Dye of Exemple XXXIX       0.80 g                                             N-[(4'-dimethylamino-2'-methoxy)                                              phenyl]-2,6-dimethyl-3-acetyl-                                                amino benzoquinoneimine    0.15 g                                             Diethanolamides of fatty acids of copra                                                                  10 g                                               Ammonia (22°Be) q.s.p. pH 9,7                                          Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied for a period of 20 minutes at ambienttemperature to bleached hair and imparts thereto a dove gray coloration.

Section C Examples of Dye Compositions Containing the Indoanilines ofFormula (I) and Other Dyes

    ______________________________________                                        (a)  N-[(4'-dimethylamino) phenyl]-3-                                              acetylamino benzoquinoneimine                                                                            0.2 g                                              Dihydrochloride of 3-nitro-4-N-(methyl-                                       β-diethylaminoethyl)- amino                                              aniline                    0.1 g                                              Ammonium lauryl sulfate    20 g                                               Triethanolamine q.s.p. pH 8.5                                                 Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied to white hair for a period of 30 minutesat ambient temperature. After rinsing, shampooing, rinsing again anddrying, the hair exhibits a linden coloration with golden glints.

    ______________________________________                                        (b)  N-[(4'-dimethylamino) phenyl]-2,6-                                            dimethyl benzoquinoneimine 0.25 g                                             2,4,6-trihydroxy-azo benzene                                                                             0.2 g                                              Ammonium lauryl sulfate    20 g                                               Triethanolamine q.s.p. pH 8.2                                                 Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied to white hair for a period of 30 minutesat ambient temperature. After rinsing, shampooing, rinsing again anddrying, the hair exhibits a canary yellow coloration.

    ______________________________________                                        (c)  N-[(4'-dimethylamino) phenyl]-2,5-                                            dimethyl benzoquinoneimine 0.3 g                                              2-amino-4,4'-dihydroxy-azo                                                    benzene                    0.2 g                                              Ammonium lauryl sulfate    20 g                                               Triethanolamine q.s.p. pH 8.8                                                 Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied to white hair for a period of about 30minutes at ambient temperature. After rinsing, shampooing, rinsing againand drying, the hair exhibits a yellow-green coloration.

    ______________________________________                                        (d)  N-[(4'-dimethylamino) phenyl]                                                 benzoquinoneimine          0.2 g                                              1,4-di-(β-morpholinoethyl) amino                                         anthraquinone              0.3 g                                              Butylglycol                5 g                                                Lauryl alcohol, oxyethylenated                                                with 10.5 moles of ethylene oxide                                                                        5 g                                                Triethanolamine q.s.p. pH 8.5                                                 Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied to white hair for a period of 30 minutesat ambient temperature. After rinsing, shampooing, rinsing again anddrying, the hair exhibits a brilliant lavender-blue coloration.

    ______________________________________                                        (e)  N-[(4'-dimethylamino) phenyl]-2,6-                                            dimethyl-3-amino benzoquinoneimine                                                                       0.2 g                                              N-[(4'-amino-2'-methoxy-5'-methyl)                                            phenyl[-3-ureido benzoquinoneimine                                                                       0.1 g                                              Butylglycol                5 g                                                Lauryl alcohol oxyethylenated with                                            10.5 moles of ethylene oxide                                                                             5 g                                                Triethanolamine q.s.p. pH 8.6                                                 Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied to white hair for a period of about 30minutes at ambient temperature. After rinsing, shampooing, rinsing againand drying, the hair exhibits a gray-green coloration.

    ______________________________________                                        (f)  Dye according to Example IX                                                                              0.2 g                                              N-[(4'-amino) phenyl]-2-6-dimethyl-                                           3-ureido benzoquinoneimine 0.1 g                                              N-[(4'-amino) phenyl]-2-methyl-5-                                             ureido benzoquinoneimine   0.1 g                                              Butylglycol                5 g                                                Lauryl alcohol oxyethylenated with                                            10.5 moles of ethylene oxide                                                                             5 g                                                Triethanolamine q.s.p. pH 9                                                   Water q.s.p.               100 g                                         ______________________________________                                    

This dye composition is applied to white hair for a period of about 30minutes at ambient temperature. After rinsing, shampooing, rinsing againand drying, the hair exhibits a parme shade.

    ______________________________________                                        (g)  N-[(4'-dimethylamino) phenyl]-2,6-                                            ditertiobutyl benzoquinoneimine                                                                          0.1 g                                              N-[(4'-hydroxy-3'-chloro) phenyl]-2-                                          chloro-5-amino benzoquinoneimine                                                                         0.1 g                                              N-[(4'-dimethylamino) phenyl]-3-                                              acetylamino benzoquinoneimine-N',N'-                                          dimethyl iminium chloride  0.1 g                                              5,6-dihydroxy indole       0.05 g                                             Butylglycol                5 g                                                Lauryl alcohol oxyethylenated with                                            10.5 moles of ethylene oxide                                                                             5 g                                                Ammonia q.s.p. pH 11                                                          Water q.s.p.               100 g                                         ______________________________________                                    

This composition is applied to white hair for a period of about 30minutes. At the end of this period, the hair is rinsed, washed withwater, rinsed again and dried. There is thus imparted to the hair asilvery-seal coloration.

What is claimed is:
 1. A dye composition for keratinic fibers comprisingan aqueous or hydroalcoholic solution of an indoaniline of the formula##SPC49##or a tautomeric form thereof wherein R₁ represents hydrogen,halogen, alkyl or alkoxy; R₂ and R₃ represent alkyl; R₄ and R₆ eachindependently represent hydrogen, halogen, alkyl, alkoxy, acetylamino,ureido, or carbalkoxyamino; and R₅ represents acetylamino, ureidocarbalkoxyamino, amino, alkylamino, hydroxy alkylamino or carbamylalkylamino, with the proviso that when R₅ represents acetylamino, R₆does not represent hydrogen; the said alkyl and alkoxy groups containing1-6 carbon atoms and said indoaniline being present in an amount of0.0075 to 2 percent by weight of said composition.
 2. The compositionaccording to claim 1 having a pH between 5 and
 11. 3. The compositionaccording to claim 1 having a pH between 7 and
 9. 4. The compositionaccording to claim 1 which also includes another direct dye for hair. 5.The composition according to claim 4 wherein said other direct dye forhair is selected from the group consisting of a nitrobenzene dye, an azodye, an anthraquinone dye, an indamine dye, an indophenol dye andanother indoaniline dye.
 6. The composition according to claim 1 whichalso contains a glycol or a wetting agent.
 7. The composition accordingto claim 1 which is a hydroalcoholic solution and also contains acosmetic film-forming resin.
 8. The composition according to claim 7wherein the alcohol is a low molecular weight alcohol.
 9. Thecomposition according to claim 7 wherein the alcohol is ethanol orisopropanol.
 10. The composition according to claim 8 wherein thealcohol is present in an amount of 20 - 70% by weight of saidcomposition.
 11. The composition according to claim 7 wherein saidcosmetic film-forming resin is present in an amount of 1 to 3% by weightof said composition.
 12. The composition according to claim 7 whereinsaid cosmetic film-forming resin is selected from the group consistingof polyvinylpyrrolidone; a copolymer of vinylpyrrolidone and vinylacetate; a copolymer of vinyl acetate and crotonic acid; a copolymer ofmaleic anhydride and butylvinylether; a terpolymer of methylmethacrylate, stearylmethacrylate and dimethylmethacrylate; and acopolymer of maleic anhydride and methylvinyl ether and the monoethylester, monoisopropyl ester and monobutyl ester thereof.
 13. Thecomposition of claim 1 present in the form of an aqueous solution, acream or a gel.
 14. A process for dyeing keratinic fibers comprisingimpregnating said fibers with an effective amount of the composition ofclaim 1 to color said fibers and after a period of contact therewithranging from about 5 to 30 minutes, rinsing the fibers, shampooing thefibers and drying the fibers.
 15. A process for coloring and settinghuman hair comprising applying to hair previously washed and rinsed, aneffective amount of the composition of claim 7, rolling the hair onrollers and then drying the hair.